Bicyclo-{8 2.2.2{9 octa-5,7-dien-2-ones and a process for their preparation

ABSTRACT

Chemical compounds having the structure:   WHEREIN Z is a moiety selected from the group consisting of:   AND WHEREIN R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are the same or different and each is selected from the group consisting of methyl and hydrogen and wherein R11 is selected from the group consisting of methyl, ethyl and hydrogen; and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzyloxyl and alkoxyl and a process for preparing such compounds involving intimately admixing a methyl substituted cyclohexadienone having the structure:   WITH ONE OF THE FOLLOWING ACETYLENIC COMPOUNDS HAVING THE STRUCTURES:   The compounds thus produced are valuable intermediates used in producing chemical compounds having valuable organoleptic properties; particularly in perfumery, in flavoring foodstuffs and in flavoring tobacco.

United States Patent Light BlCYCLO-[2.2.2]OCTA-5,7-DlEN-2-ONES AND A PROCESS FOR THEIR PREPARATION Kenneth K. Light, Asbury Park, NJ.

International Flavors & Fragrances Inc., New York, NY.

Filed: Jan. 28, 1974 App]. No.: 436,847

Inventor:

Assignee:

U.S. Cl 260/586 C; 131/17 R; 252/522; 260/395; 260/586 R; 260/586 G; 260/611 A; 260/614 R; 260/617 R; 260/617 F;

260/63l.5; 260/632 Y; 260/654 R; 424/59; 424/65; 424/69; 424/70; 424/76; 426/171; 426/175; 426/805 Int. Cl C070 45/00; CO7c 49/54 Field of Search 260/586 R, 590

[56] References Cited UNITED STATES PATENTS 3/1965 Barton et a1. 260/586 R 1/1973 Schmid 260/586 R OTHER PUBLICATIONS Alder et 211., Berichte, Vol. 90, pp. 1709-1720, (1957).

Primary Examiner-Bernard Helfin Assistant E.\'aminerNorman Morgenstern Attorney. Agent. or Firm-Arthur L. Liberman, Esq.; Harold Haidt, Esq.

[57'] ABSTRACT Chemical compounds having the structure:

wherein Z is a moiety selected from the group consisting of:

and

[451 Apr. 22, 1975 and wherein R R R R R R R R R and R are the same or different and each is selected from the group consisting of methyl and hydrogen and wherein R is selected fromthe group consisting of methyl, ethyl and hydrogen; and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzyloxyl and alkoxyl and a process for preparing such compounds involving intimately admixing a methyl substituted cyclohexadienone having the structure:

with one of the following acetylenic compounds having the structures:

The compounds thus produced are valuable intermediates used in producing chemical compounds having valuable organoleptic properties; particularly in perfumery, in flavoring foodstuffs and in flavoring tobacco.

22 Claims, No Drawings BICYCLO-[2.2.2DCTA-5,7-DIEN-2-ONES AND A PROCESS FOR THEIR PREPARATION BACKGROUND OF THE INVENTION Materials which can provide patchouli-like, amber and woody fragrance notes are known in the art of perfumery. Many of the natural materials which provide such fragrances and contribute desired nuances to perfumery compositions are high in cost, vary in quality.

from one batch to another and/or are generally subject to the usual variations of natural products.

There is accordingly a continuing effort to find synthetic materials which will replace the essential fragrance notes provided by natural essential oils or compositions thereof. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the compositions. The search for materials which can provide a more refined patchoulilike fragrance has been difficult and relatively costly in the areas of both natural products and synthetic products.

ln addition, artifical flavoring agents for foodstuffs have received increasing attention in recent years. In many years, such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished cost and their reproducible flavor qualities. For example, natural food flavoring agents such as extracts, concentrates, and the like are often subject to wide variations clue to changes in the quality, type and treatment of the raw materials. Such variations can be reflected in the end product and result in unfavorable flavor characteristics in said end product. Additionally, the presence of the natural product in the ultimate food may be undesirable because of increase tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips, sausages, gravies and the like are apt to be stored prior to use.

The fundamental problem in creating artifical flavor agents is that the artifical flavor to be achieved be as natural as possible. This generally proves to be a difficult task since the mechanism for flavor development in many food is not completely known. This is noticable in products having woody-balsamic, fresh walnutkernel and walnut-skin flavor characteristics.

Reproduction of woody-balsamic, fresh walnutkernel and walnut-skin flavor and aroma has been the subject of long and continuing searches by those engaged in a production of foodstuffs and beverages. The severe shortage of food in many parts of the world has given rise to the development of previously unused sources of protein which are unpalatable. Accordingly, the need has arisen for the use of flavoring materials which will make such sources of protein palatable to human sensory organs.

Even more desirable is a product that can serve to substitute for difflcult-to-obtain natural perfumery oils and at the same time substitute for natural flavoring ingredients in both foodstuffs as well as in tobacco.

1972, pages 2871-2877 discloses the preparation of patchouli alcohol having the structure:

Patchouli alcohol is shown to be prepared via the reaction sequence:

An article by Corey and Wipke entitled Computer- Assisted Design of Complex Organic Synthese appearing in 166 Science 178 (1969) sets forth, interalia, the sequence of reactions leading to compounds having the structures:

2 1 h ..0H .LoH 0" Indeed, economic syntheses of patchouli alcohol itself and *g do not appear to be given in the literature. Danishevsky and Dumas 1968 Chemical Communication, Pages 1287-1288 discloses the synthesis of ra- One of these reacnon Sequences Involves Performmg 5 cemic patchouli alcohol and epi patchouli alcohol havthe reacnons: ing the structure:

by means of cyclization of a compound having the structure:

However, syntheses of methyl homologues and double bond analogues of patchouli alcohol and dihydropatch- 40 This material is indicated to be prepared according to ouli alcohol have not yet been disclosed in the prior art. the following rather complex reaction sequence:

Continued The processes and intermediates of our invention give rise to reaction products having properties considered to be unobvious, unexpected and advantageous with respect to the properties of prior-art compounds.

THE INVENTION As set forth in copending U.S. patent application Ser. No. 436,848, filed Jan. 28, 1974; it has been determined that certain tricyclic alcohols are capable of imparting a variety of flavors and fragrances to various consumable materials. Briefly, our invention contemplates a process for producing intermediates used in synthesizing such tricyclic alcohols which, in turn, are useful for altering the flavors and/or fragrances of such consumable materials by adding thereto a small but effective amount of at least one tricycle alcohol having either the structure:

wherein the dotted line can be a carbon-carbon single bond or a carbon-carbon double bond; and each of R R R R R R R R R and R is the same or different and each represents hydrogen or methyl and wherein R is hydrogen, methyl or ethyl with the proviso that the dashed line is a carbon-carbon single bond when one of R or R is hydrogen.

The tricyclic alcohols produced using, interalia, the process of my invention are actually reacemic mixture rather than individual steroisomers, such as the case concerning isomers of patchoulic alcohol which are so obtained from patchouli oil.

Specific examples of end products of my synthesis which have been found to be useful are as follows:

A. The compound having the structure:

This compound has a warmm patchouli-like fragrance aroma and a woody-balsamic, walnut-kernel and walnut-skin like taste in food flavors.

- ot l This compound has a warn patchouli fragrance and a wherein X may be either hydroxyl, bromo, chloro, benzyloxyl, and alkoxyl thereby forming a diene compound having the structure:

wherein Z is one of the moieties:

Compounds having the structure:

are novel compounds. In this reaction, it is best to proceed at a temperature in the range of 200-260C with the most preferred temperature being 220C. The reaction may be carried out in the presence of an inert solvent such as benzene, hexane or cyclohexane (or any other inert solvent) or the reaction may be carried out in the absence of solvent. Although, either the acetylenic compound or the cyclohexadienone may be used in excess, it is preferred to use equimolar quantities of each reactant.

The above-mentioned novel diene compound which is also within the scope of my invention may then be hydrogenated with hydrogen in the presence of a catalyst such as palladium, platinum, nickel or other suitable hydrogenation catalyst.

The reaction temperature may be from 20-220C with a temperature range of l00-200being preferred. The reaction is preferably carried out at superatmospheric pressures and pressures in the range of 1-150 atomspheres are suitable. Preferred pressures range from 5-150 atmospheres.

The hydrogenation reaction gives rise product having the structure:

to a ketone but it is noteworthy that the compound produced is one where the dashed line is a carbon-carbon single bond if one of R or R is hydrogen and the compound primarily produced is one where the dashed line is a carbon-carbon double bond if R and R are both methyl. Where R is methyl or ethyl, a reaction pressure of greater than 130 atmospheres is preferred.

When X is bromo or chloro, the ketone thus produced may then be immediately cyclized by treating same with an alkali metal selected from the group consisting of sodium, potassium or lithium. The cyclization may be carried out in diethyl ether, tetrahydrofuran or benzene, The reaction temperature preferred is the reflux temperature of the reaction mass at atmospheric pressure and is a function of the solvent used. Thus, for example, when using tetrahydrofuran solvent, the cyclization reaction temperature is approximately 65C. The reaction can be carried out at temperatures ranging from C up to 100C. For the cyclization, the mole ratio of ketone to metal is preferably 7:1 although mole ratio of ketone to metal is from 1:1 up to 10:1 may be used.

Prior to cyclization, in the event that X is OH, the ketone must be halogenated with thionyl chloride or any other suitable halogenating agent, for example, thionyl ch1oride-pyridine complex, phosphorous trichloride, phosphorous tribromide, aqueous HCl or aqueous l-lBr. The halogenation reaction may be carried out in the presence or in the absence of an inert solvent such as benzene, toluene, cyclohexane or pyridine. The reaction temperature may range from 20C up to 100C with a reaction temperature of 80C being preferred. The mole ratio of halogenating agent2ketone of 3:1 is preferred when using thionyl chloride and a ratio of 5 :1 is preferred when using aqueous HC1 and l-lBr.

1n the event that X is benzyloxyl or alkoxyl, such ether must first be cleaved or hydrolyzed to form the corresponding alcohol which, in turn, must be halogenated as described in the immediately preceding para- 10 graph. Thus, cleavage of the ether may be carried out using refluxing hydriodic acid or refluxing hydrobromic acid in acetic acid.

The aforementioned alkyl ethers and benzyl ethers are preferably produced by means of one of three techniques, all using the Williamson synethesis, J. Chem.

Soc., 87 605 (1905):

i. Reaction of an acetylenic compound as described above where X is chloro, bromo or iodo (e.g., pent- 4-n-1-iodide) with either an alkali metal alkylate (e.g., sodium propoxide) or an alkali metal benzylate (e.g., potassium benzylate); or

ii. Reaction of an alkali metal oxide of an acetylenic compound as described above where X is hydroxyl (e.g., potassium pent-4-yn-l-oxide) with an alkyl halide (e.g., ethyl bromide) or a benzyl halide (e.g., benzyl chloride); or

iii. Reaction of a chloro alkyl ether of an alkanol (e.g., 3-chloropropyl butyl ether) with an alkali metal acetylide (e.g., sodium acetylide).

The initial reaction may utilize, for example, the following reactants:

a. Acetylenic compounds:

2,2,3 ,3-Tetramethylpent-4-yn- 1 -ol 3-Methylpent-4-yn-l-ol 2,2,5-Trimethylhex-3-yn-l-chloride 3-Mentylpent-4-yn- 1 -chloride 2,2-Dimethylhex-3-yn-l-chloride 3 -Methylpent-4-ynl -bromide Pent-3-yn- 1 -ol Pent-4-yn- 1 -ol Pent-3-ynl -chloride Pent-4-ynl -chloride 2-Methy1hex-3-yn-l-bromide Pent-4-yn-l-bromide Hex-3-yn-lchloride 2,2,3,3-Tetramethylpent-4-yn-l-yl n-propyl ether 3-Methylpent-4-yn-l-yl benzyl ether 2,2,5-Trimethy1hex-3-yn-l-yl ethyl ether 3-Methylpent-4-yn-l-yl methyl ether 2,2-Dimethylhex-3-yn-l-yl ethyl ether 3-Methylpent-4-yn-l-yl n-hexyl ether Pent-3-ynl -y] n-heptyl ether Pent-4-yn- 1 -y] n-butyl ether Pent-3-yn-l-yl n-propyl ether Pent-4-yn-l-yl i-propyl ether 2-MethylheX-3-yn-l-y1 ethyl ether Pent-4-ynl -y1 benzyl ether Hex-3-yn-l-yl benzyl ether b. Cyclohexadienone compounds:

2,6,6-Trimethylcyclohexadien- 1 -one 2,3,4,5,6,6-Hexamethylcyclohexadien-l-one 2,3 ,4,6,6-Pentamethylcyclohexadien- 1 -one 6,6-Dimethylcyclohexadien-l -one 4,5 ,6,6-Tetramethylcyc1ohexadien- 1 -one 2,4,5 ,6 ,6-Pentamethylcyclohexadien- 1 -one When the final cyclization reaction is completed, the

reaction mixture is worked-up using routine purification procedures including the unit operations of extraction, crystallization, drying and/or distillation.

The individual tricyclic compounds produced using, interalia, the process of my invention can be obtained in puruer form or in substantially pure form by conventional purification techniques. Thus, the products can be purified and/or isolated by distillation, extraction, crystallization, preparative chromatographic techniques, and the like. It has been found desirable to purify the tricyclic compounds by fractional distillation under vacuum.

It will be appreciated from the present disclosure that the tricyclic compounds and mixtures thereof produced using, interalia, the process of my invention can be used alter, vary, fortify, modify, enhance or otherwise improve the flavor of a wide variety of materials which are ingested, consumed, or otherwise organoleptically sensed.

The term alter in its various forms will be understood herein to mean the supplying or imparting of a flavor character or note to an otherwise bland, relatively tasteless substance, or augmenting an existing flavor characteristic where the natural flavor is deficient in some regard or supplementing the existing flavor impression to modify the organoleptic character.

Such compounds are accordingly useful in flavoring compositions. A flavoring composition is taken to mean one which contributes a part of the overall flavor impression by supplementing or fortifying a natural or artificial flavor in a material or one which supplies substantially all the flavor and/or aroma character to a consumable article.

The term foodstuff as used herein includes both solid and liquid ingestible materials for man or animals, which materials usually do, but need not, have nutritional value. Thus, foodstuffs includes meats, gravies, soups, convenience foods, malt, alcoholic, and other beverages, mile and dairy products, seafoods including fish, crustaceans, mollusks, and the like, candies, vegetables, cereals, soft drinks, snacks, dog and cat food, other veterinary products, and the like.

The term tobacco will be understood herein to mean natural products such as, for example, burley, Turkish tobacco, Maryland tobacco, flue-cured tobacco and the like including tobacco-like or tobaccobased products such as reconstituted or homogenized leaf and the like, as well as tobacco substitutes intended to replace natural tobacco, such as lettuce and cabbage leaves and the like. The tobaccos and tobacco products include those designed or used for smoking such as in cigarette, cigar, and pipe tobacco, as well as products such as snuff, chewing tobacco and the like.

When the tricyclic compounds produced using, interalia, the process of my invention are used in a flavoring composition, they can be combined with conventional flavoring materials or adjuvants. Such co-ingredients or flavoring adjuvants are well known in the art for such use and have been extensively described in the literature. Apart from the requirement that any such adjuvant material be ingestibly acceptable, and thus nontoxic or otherwise non-deleterious, conventional materials can be used and broadly include other flavor materials, vehicles, stabilizers, thickeners, surface active agents, conditioners and flavor intensifiers.

Such conventional flavoring materials include satuacids; alcohols, including primary and secondary alcohols; esters; carbonyl compounds including ketones and aldehydes; lactones; other cyclic organic materials including benzene derivatives, alicyclic compounds, heterocyclics such as furans, pyridines, pyrazines and the like; sulfur-containing materials including thiols, sulfides, disulfides and the like; proteins; lipids carbohydrates; so-called flavor potentiators such as monosodium glutamate, guanylates, and inosinates; natural flavoring materials such as cocoa, vanilla, and caramel; essential oils and extracts such as anise oil; clove oil; and the like; and artificial flavoring materials such as vanillin; and the like.

Specific flavor adjuvants are as follows:

EthyI-Z-methyl butyrate;

Vanillin;

Butyl valerate;

2,3-Diethyl pyrazine;

Methyl cyclopentenolone;

Benzaldehyde;

Valerian oil Indian; and

Propylene glycol The tricyclic compounds produced using interalia, the process of my invention can be used to contribute warm, patchouli-like aromas. As olfactory agents the tricyclic compounds of my invention can be formulated into or used as components of a perfume composition.

The term perfume composition is used herein to mean a mixture of organic compounds, including, for example, alcohols, aldehydes, ketones, nitriles, esters, and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain: (a) the main note of the bouquet or foundation-stone of the composition; (b) modifiers which round-off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation; and (d) top-notes which are usually lowboiling fresh smelling materials.

In perfume compositions the individual component will contribute its particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of each ingredient. Thus, the individual compounds of this invention, or mixtures thereof, can be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient in the composition.

The amount of the tricyclic compounds produced using, interalia, the process of my invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 2 percent of the tricyclic compounds produced used, interalia, the process of my invention, or even less, can be used to impart a patchouli scent to soaps, cosmetics, and the other products. The amount employed can range up to 50% or higher and will depend on considerations of cost, nature of the end product, the effect de-.

sired on the finished product and particular fragrance sought.

The tricyclic compounds produced using, interalia, the process of my invention can be used alone or in a perfume composition as an olfactory component in detergents and soaps, space odorants and deodorants; perfumes; colognes; toilet waters; bath salts; hair preparations such as lacquers, brilliantines, pomades, and

shampoos; cosmetic preparations such as creams, de-

odorants, hand lotions, and sun screens; powders such as talcs, dusting powders, face powder, and the like. When used as an olfactory component of a perfumed article, as little as 0.01 percent of one or more of the tricyclic compounds will suffice to impart a warm pal0 tchouli aroma. Generally, no more than 0.5 percent is required.

In addition, the perfume composition can contain a vehicle or carrier for the tricyclic compounds alone or with other ingredients. The vehicle can be a liquid such as an alcohol such as ethanol, 21 glycol such as propylene glycol, or the like. The carrier can be an absorbent solid such as a gum or components for encapsulating the composition.

The following examples are given to illustrate embodiments of my invention as it is presently preferred to practice it as well as means for utilizing same. It will be understood that these examples are illustrative, andthe invention is not to be considered as restricted 2 thereto except as indicated in the appended claims.

EXAMPLE I Preparation of 3,3-dimethy1-6-(3-ch1oropropy1)-bicyclo-[2,2,2]octa- 5,7-diene-2-one Into an autoclave, 28 gm. of 6,6-dimethy1cyclohexadienel-one, 28 gm. of S-chloro-l-pentyne and 300 m1 of benzene are added. The autoclave is sealed and the reaction mass is heated to 220C. The reaction is car- 3 ried out over a period of 4 hours after which time the reaction mass is cooled to C. The reaction mass is then removed from the autoclave and the resultant product is stripped of benzene and distilled at a vapor temperature of l36-138C and 3.03.2 mm. Hg. pres- 40 sure. The structure of the resultant product is confirmed by NMR, IR and mass spectral analyses to be 3,- 3-dimethyl-6-(3-chloropropyl)-bicyclo-[2.2.2]-octa- 5,7-diene-2-one.

EXAMPLE II Preparation of 3 ,3-dimethyl-6-( 3-chloropropyl)-bicyclo-[ 2.2.2]- octan-2-oue Into an autoclave are placed 20 gm. of 3,3-dimethyl- 6-(3-chloropropyl)-bicyc1o-[2.2.2]-octa-5,7-diene- 2-one produced by the process of Example I and, in addition, 300 ml ethyl alcohol and 1 gm. of palladiumcarbon catalyst. The autoclave is sealed and then charged with hydrogen at a pressure of 200 pounds per square inch. The reaction mass is stirred for a period of 5 hours at a temperature of 100-115C during which period the pressure in the autoclave varies from 240 up to 260 pounds per square inch. The autoclave is then cooled and the product is removed and distilled. Two products are obtained. The first has a boiling point of 90100C at 1.5 mm. Hg. pressure and is shown by IR, MS and NMR to be 3,3-dimethyl-6-propy1-bicyclo- [2.2.2]-octane-5-one. The second is the desired material, 3,3-dimethy1-6-(3-ch1oropropy1)-bicyc1o-[2.2.2]- oc'tan-Z-one with a boiling point of 131C at 1.5 mm. Hg. pressure weighing 8.2 grns.

EXAMPLE I11 Preparation of octahydro-9,9-dimethyll ,6-methanonaphthalene- 1 (2H)-o1' Into a 250 ml three-nech flask equipped with stirrer, thermometer and reflux condenser, the following materials are placed:

Sodium spheres 1.5 gm. Tetrahydrofuran 50.0 ml 3,3-dimethyl-6-(3-ch1oropropy1)- 1.4 gm.

The reaction mass is refluxed for a period of 4 hours and allowed to stand overnight. The liquid phase is separated from the sodium spheres. The liquid phase is then washed with 100 ml water and acidified with dilute hydrochloric acid. The resultant material is extracted twice with diethyl ether. The combined ether phases are washed with saturated aqueous NaHCO and then dried over anhydrous magnesium sulfate. The solution is stripped of solvent and the remaining residue is separated on a GLC column:

4; inch X 4 feet, 20% SE-30 (a methyl silicone oil available from Analabs, Inc. of P0. 501, North Haven, Connecticut 06473); l00220C at 8C/min) The structure of the major product of the reaction (43% by GLC) was shown to be the title material.

Mass Spectral Analysis is as follows: 41, 55, 84, 97, 133, and l 10.

NMR Analysis is as follows: 1.06(s,6H), complex signals from 1.0 to 2.1 ppm.

EXAMPLE IV Preparation of 1,3,3-trimethy1-6-( 1-methyl-3-hydroxypropyl )-bicyclo- [2.2.2 ]-octa-5,7-dien-2-one A solution of 27.2 gm. (0.20 ml) of 2,6,6- trimethylcyclohexadien-l-one and 28 gm. (0.28 ml) of 3-methyIpent-4-yn-l-ol in 300 cc of benzene is placed in a 2 liter stirred autoclave and heated to 220C for 5 hours. At the end of this time, GLC shows no trimethylcyclohexadien-l-one remaining and the solvent is removed under vacuum and the residue is distilled to yield about 37 gm. of the product, 1,3,- 3-trimethy1-6-( l-methyl-3-hydroxypropyl)-bicyc1o- [2.2.21-octa-5,7-dien-2-one.

EXAMPLE V Preparation of 1,3,3-trimethy1-6-(1-methyl-3-hydroxypropyl)-bicyc1o- [2.2.2]-octan-2-one Into a stirred autoclave, 30 gm. (0.13 ml) of 1,3,3- trimethyl-6-(1-methyl-3-hydroxypropy1)-bicyclo- [2.2.2]-octa-5,7-dien-2-one, 0.5 gm. of 5% of palladi urn-carbon and 300 m1 of isopropyl alcohol is added. The autoclave is pressurized to 400 pounds per square inch with hydrogen and heated to 100C for 6 hours. At the end of this time, the mixture is filtered, stripped of solvent and vacuum distilled, yielding about 27 gm. of the product, 1,3,3-trimethyl-6-(l-methy1-3- hydroxypropyl)-bicyclo-[2.2.2]-octan-2-one.

EXAMPLE VI Preparation of l,3,3-trimethyl-6-( l-methyl-3-chloropropyl)-bicyc1o- [2.2.21-octan-2-one A mixture of 25 gm. (0.105 mole) of 1,3,3-trimethyl- 1 6-( 1-methyl-3-hydroxypropyl)-bicyclo-[2.2.2]-octan- 2-one and 40 gm. of thionylchloride is gently refluxed for two hours. The excess thionylchloride is stripped off and the residue is distilled to yield about 20 gm. (80%) of the product, I,3,3-trimethyl-6-( l-methyl-3- chloropropyl)-bicycIo-[2.2.21-octan-2-one.

EXAMPLE VII Preparation of Patchouli Alcohol A sodium sand is prepared by heating 1 1.5 gm. of sodium in xylene and stirring. The xylene is decanted and replaced by 300 cc of anhydrous tetrahydrofuran. A solution of 20 gm. (0.078 mole) of 1,3,3-trimethyl-6- l-methyI-3-chloropropyl)-bicycIo-[2.2.2]-octan- 2-one in 50 cc of tetrahydrofuran is added with stirring at room temperature over a 15 minute period. A slight exotherm occured during addition. The solution is brought to reflux and held there for 3 hours. At the end of this time, the solution is decanted from the excess sodium and is acidified with 5% I-ICI. The excess acid is neutralized by a single wash with saturated sodium bicarbonate solution. The solution is dried over magnesium sulfate, filtered and stripped, yielding a residue which is recrystallized from hexane to yield about 10 gm. (50%) of racemic patchouli alcohol, mp 39-40 having the structure:

EXAMPLE VIII Perfume Formulation The following woody cologne" perfume formulation is prepared:

Ingredients Parts by Weight Bcrgamot oil 150 Orange oil 200 Lemon oil 50 Eugenol l0 4-(4-mcthyl-4-hydroxy amyl) A cyclohexcnc carboxaldehydc 40 Ylang 2 Petitgrain Paraguay l0 Gamma mcthyl iononc 20 according to Example Ill Octahydro-9,9-dimethyl-l ,6-methanonaphthalenel (2H)-ol imparts a warm patchouli-like character to this woody cologne composition.

EXAMPLE IX preparation of a Soap Composition A total of 100 gm. of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil are mixed with 1 gm. of the perfume composition set forth in Exampel VIII until a substantially homogeneous composition is obtained. The soap composition manifests a characteristic woody cologne perfumed sodium base toilet soap made from tallow and coconut oil is mixed with 1 gm. of octahydro-9,9- dimethyll -methanonaphthalene-l-(2H )-ol until a substantially homogeneous composition is obtained. The soap composition manifests a warm patchouli-like character.

EXAMPLE XI Preparation of a Detergent Composition 20 A total of 100 gm. of a detergent powder sold under the trademark RINSO are mixed with 0.15 gm. of a perfume composition containing the mixture obtained in Example VIII until a substantially homogeneous composition having a woody cologne fragrance with a warm patchouli-like character is obtained.

EXAMPLE x11 Preparation of a Cosmetic Base EXAMPLE XIII Liquid Detergent Containing octahydro-9,9-dimethyl-l ,6-methanonaphthalenel (2H )-ol Concentrated liquid detergents with a patchouli-like odor containing 0.2%, 0.5% and l.2%-of the product produced in accordance with the process of Example III, octahydro-9,9-dimethyl-l,6-methanonaphthalenel-(2l-I)-ol, are prepared by adding the appropriate quantity of octahydro-9,9-dimethyl-l ,6- methanonaphthalene-l-(2I-I)-ol to the liquid detergent known as P-87. The patchouli aroma of the liquid detergent increases with increasing concentration of the octahydro-9,9-dimethyl-l ,6-methanonaphthalene- I (2H)-ol of this invention.

EXAMPLE XIV Preparation of Cologne and Handkerchief Perfume The composition of Example VIII is incorporated in a cologne having a concentration of 2.5% in aque- 5 ous ethanol; and into a handkerchief perfume in a concentration of 20% (in ethanol). The use of the composition of Example VIII affords a distinct and definite woody cologne aroma having a warm patchouli- Propylene Glycol like character to the handkerchief perfume and to the cologne.

EXAMPLE XV Cologne and Handkerchief Perfume The octahydro-9,9-dimethyl-l .6-methanonaphthalene-l-(2l-I)-ol produced by the process of Example 111 is incorporated into a cologne having a concentration of 2.5% in 85% ethanol; and into a handkerchief perfume in a concentration of (in 95% ethanol). The octahydro-9,9-dimethyl-l ,6-methanonaphthalenel (2H)-ol produced in Example III affords a distinct and definite warm patchouli-like aroma to the handkerchief perfume and to the cologne.

EXAMPLE XVI Flavor Composition The following basic walnut flavor formulation is prepared:

lngredients Parts by Weight EthyI-Z-Methyl Butyrate 10 Vanillin 40 Butyl Valerate 40 2,3-Diethyl Pyrazine 5 Methyl Cyclopentcnolone 80 Benzaldehyde 60 Valerian Oil Indian 0.5 (1% in 95% aqueous ethanol alcohol) Octahydro-9,9-dimethyl-l ,6-methanonaphthalene-1- (2H)-ol produced by the process of Example 111 is added to the above formulation at the rate of 1.5%. This formulation is compared to a formulation which does not have octahydro-9,9-dimethyl-l ,6- methanonaphthalene-l-(2H)-ol added to it, at the rate of 20 ppm in water. The formulation containing octahydro-9,9-dimethyl-l ,6-methanonaphthalenel -(2I-I )-ol has a woody-balsamic, fresh walnut kernel and walnut skin-like taste and, in addition, has a fuller mouthfeel and longer lasting tast. The flavor that has added to it, octahydro-9,9-dimethyl-l,-methanonaphthalene-l-(2H)-ol, is preferred by a group of flavor panelists, and they consider it to be a substantially improved walnut flavor.

EXAMPLE XVII Beverage The addition of octahydro-9,9-dimethyl-l ,6- methanonaphthalene-l-(2H)-ol prepared by the process of Example III at the rate of 0.3 ppm to a commercial Cola beverage gives the beverage a fuller woodybalsamic long lasting taste and adds to the pleasant top notes of the beverage. When comparing the Cola beverage containing octahydor-9,9-dimethyl-l ,6- methanonaphthalene1-(2H)-ol to one having the same formula but not containing octahydro-9,9-dimethyll,6-methanonaphthalene-1-(2H)-ol, a five member bench panel prefers the beverage containing the octahydr09,9-dimethyl-l ,6-methanonaphthalenel 2I-I)-ol.

EXAMPLE XVIII Tobacco Flavor Formulation Cigarettes are produced using the following tobacco formulation:

At the rate of 0.2%, the following tobacco flavor formulation is applied to all of the cigarettes produced with the above tobacco formulation.

Ingredients Parts by Weight Ethyl Butyrate .05 Ethyl Valeratc .05 Maltol 2.00 Cocoa Extract 26.00 Coffee Extract 10.00 Ethyl Alcohol 20.00 H O 41.90

To 50% of the cigarettes, 10 and 20 ppm of octahydro-9,9-dimethyl-l ,6-methanonaphthalene-1-(2H)-ol are added. These cigarettes are hereinafter called experimental cigarettes and the cigarettes without the octahydro-9,9-dimethyl-l ,-methanonaphthalene- 1 -(2H 0] are hereinafter called control cigarettes. The control and experimental cigarettes are then evaluated by paired comparison and the results are as follows:

a. In aroms, the experimental cigarettes are found to be more aromatic.

b. In smoke flavor, the experimental cigarettes are found to be more aromatic, more sweet, more bitter, more green, richer and slightly less harsh in the mouth and more cigarette tobacco-like than the control cigarettes.

The experimental cigarettes containing 20 ppm of octahydro-9,9-dimethyll ,6-methanonaphthalenel (2H)-ol are found to be woody, slightly chemical and mouth-coating in the smoke flavor.

All cigarettes both control and experimental, are evaluated for a smoke flavor with 20 mm cellulose acetate filter. Octahydro-9,9-dimethyl-l ,6- methanonaphthalene-l-(2H)-o1 enhances the tobaccolike taste of the blended cigarette.

EXAMPLE XIX Preparation of 3,3,4,7,8-hexamethyl-6-(3-hydroxypropyl)-bicyclo- (2.2.2)-octa-5,7-dien-2-one Into a two liter autoclave, the following ingredients are placed:

Ingredients Parts by Weight 2,2,3,4,5,6-Hexamethyl-Cyclo- 63.1 gm. hexa-3,5-dien-l-one 4-Pentyn-l-ol 29.7 gm. Benzene 300.0 ml

1.40 (s,6I-I), 1.66 (s,3I-I), 1.76 (s,3I-I), 2.10 (m,2I-I), 3,64 (t,2I-I), 5.72 (m,lI-I) ppm.

EXAMPLE XX Preparation of 3 ,3,4,7,8-I-Iexamethyl-6-( 3-hydroxypropyl)-bicyclo- 2.2.2. )-oct-7-en-2-one l5 Into a 2 liter autoclave, the following ingredients are placed:

Ingredients Parts by Weight l,3,3,4,7,8-hexamethyl-6-(3-hydroxy- 50 gm.

propyl)-bicyclo-(2.2.2)-octa-5,7-

dien-2-one 5% Palladium on carbon 1 gm.

lsopropyl alcohol EXAMPLE XXI Preparation of 1,3 ,3 ,4,7,8-hexamethyI-6-( 3-chloropropyl Bicyclo-( 2.2.2. )-oct-7-en-2-one Into a 250 ml three-neck flask equipped with dropping funnel, nitrogen inlet tube, thermometer and reflux condenser, the following materials are placed:

Ingredients Parts by Weight Pyridine 115 gm. l.3,3,4,7.8-hexamethyl-6-( 3-hydroxy 13.0 gm.

propyl )-bicyclo-( 2.2.2 )-oct-7-en-2-one 16.0 gm of thionyl chloride is added dropwise with stirring to the reaction mass over a period of 25 minutes. During this times, the reaction mass temperature rises rapidly and is controlled by the use of an ice bath so as not to exceed 50C.

After the addition of the thionyl chloride is completed, 5.8 gm. of pyridine and then an additional 8.0 gm. of thionyl chloride is added while maintaining the temperature of the reaction mass at 40C. The reaction mass is then stirred for a period of 3 hours at room temperature and is then extracted with seven 40 ml portions of diethyl ether. The combined ether extracts are then stripped on a rotary evaporator. The resulting residue is washed with 100 ml of water. Methylene chloride is added to facilitate separation of the resulting aqueous and organic layers. The water wash is backextracted with methylene chloride and the combined methylene chloride phases are washed over once more with water and then dried and stripped. The resulting residue weighs 27.4 gm. Mass spectral and IR analyses yield information that the resulting product is the title compound.

Ingredients Mass spectral analysis is as follows: m/e 135, 178, 41, 212 282 (Parent peak).

EXAMPLE XXII Preparation of I-Iexahydrohexamethylmethanonaphthalenol Into a 250 ml three neck flask equipped with stirrer, thermometer, reflux condenser, heating mantle and nitrogen inlet tube, the following ingredients are placed:

Ingredients Parts by Weight Sodium sand produced by vigorously 2.2 gm. shaking sodium spheres in hot xylene Tetrahydrofuran 75.0 ml l.3,3,4,7,8-hexamethyl-6-(3-chloropropyl) 2.0 gm.

bicyclo-( 2.2.2 )-oct-7-en-2-one The reaction mass is stirred at reflux for a period of 30 minutes. After the 30 minute period, the sodium sand coagulates into one lump. Stirring is continued at reflux for a period of 3 additional hours. The mixture is then cooled and the liquid is decanted from the sodium. The reaction product is then added to ml of water and the mixture is acidified to a pH of 3 with 5% hydrochloric acid. 50 ml of diethyl ether is then added and the layers are then separated. The aqueous layer is extracted once with 50 ml of diethyl ether. The ether layers are combined and are washed (i) with water, followed by (ii) saturated sodium bicarbonate solution, and then (iii) water. The diethyl ether solution is then dried over anhydrous magnesium sulfate and then stripped on a rotary evaporator yielding 2.0 gm. of product. Mass spectral, IR, NMR and GLC analyses yield the information that the major product is the title compound, having the structure:

EXAMPLE XXIII Preparation of l,3,3-trimethyl-6-( 3-hydroxypropyl)-Bicyclo-( 2.2.2 octa-5,7-dien-2-one Into a 2 liter autoclave, the following ingredients are added:

Parts by Weight 2,2,6-Trimethyl cyclohexadienone 25.0 gm. -Pentyn-I'ol 25.0 gm. Brenzene 300.0 mil The autoclave is sealed and the reaction mass is stirred for a period of 12 /2 hours at 220C. The reaction mass is then removed from the autoclave and stripped of solvent on a rotary evaporator. A GLC sample of the material shows no 2,2,6-trimethylcyclohexadienone remaining (/ainch X feet, 10% carbowax; 80C- 220C at 8C/min.). The residue (58.1 gm.) is rush distilled on a micro vigreaux column under vacuum, yielding 29.8 gm. of a product of boiling point 150C at 1.5 mm. Hg. pressure. Mass spectral, IR and NMR analyses yield the information that the product is the title compound.

Mass spectral analysis is as follows: m/e 70, 105, 106, 42, 117, 91.

Infra-red analysis shows a characteristic peak at 1709 cm.

NMR analysis is as follows: 1.06 (s, 6H), 1.45 (s, 3H), 1.70 (m, 2H), 2.17 (m, 2H), 3.40 m,1H), 3.62 t, 2H), 6.05 (m, 2H), 6.53 (t, 1H)

EXAMPLE XXIV Preparation of 1,3,3-trimethyl-6-(3-hydroxypropy1)-Bicyclo(2.2.2)- octan-2-one Into a 2 liter autoclave, the following ingredients are added:

Ingredients Parts by Weight 5% Platinum on carbon, prereduced 0.5 gm. 1,3,3-trimcthy1-6-( 3-hydroxypropyl)- 27.8 gm. bicyclo-(2.2.2)-octa-5,7-dicn-2-one lsopropyl alcohol EXAMPLE XXV Preparation of 1,3 ,3-trimethyl-6-( 3-chloropropyl-Bicyclo-(2.2.2 octan-Z-one Into a 50 ml flask equipped with reflux condenser, thermometer and addition funnel, the following ingredients are added:

Parts by Weight Ingredients 1,3,3-Trimethyl-6-( 3-hydroxypropyl)- 13.8 gm. bicyclo-( 2.2.2 )-octan-2-one Benzene 6.0 ml.

14 gm. of thionyl chloride is added to the reaction mass over a period of 5 minutes with stirring, the addition causing an exothermic reaction. The reaction mass temperature rises to 55C. Following addition, the mixture is stirred for 3 hours at reflux. The pot temperature is initially 92C at reflux, but rises to 100C after a period of 3 hours.

After cooling, the mixture is poured onto 100 gm. of ice. The resulting ice mixture is then allowed to warm to room temperature and is then neutralized with sodium bicarbonate and the reaction mass-ice mixture is extracted 4 times with diethyl ether. The combined ether extracts are dried over anhydrous magnesium sulfate and filtered. The ether is then stripped on a rotary evaporator yielding 14.4 gm. of residue. The residue is rush-distilled on a micro vigreaux column at a temperature of l43l44C at a pressure of 1.2 mm. Hg. Mass spectral, IR and NMR analyses yield the data that the product is the title compound.

Mass spectral analysis is as follows: m/e 82, 170, 171, 41, 242 (Parent peak).

NMR analysis is as follows: 0.91 (s, 3H), 1.07 (s, 3H), 1.11 (s, 3H), l.4-2.1 (signal for 12H), 3.47 (t, 2H) ppm.

EXAMPLE XXVI Synthesis of Dihydronorpatchoulinol Ingredients Parts by Weight Xylene 15 ml Sodium 7.5 gm.

The mixture is heated to C while stirring vigorously. When the sodium is completely dispersed in fine particles, the stirring is ceased and the heat source is removed after which time the mixture is cooled using an ice bath. When the sodium dispersion temperature reaches 30C, the xylene isdecanted and replaced with 50 gms. of tetrahydrofuran. The resulting mixture is refluxed and 11 gm. of 1,3,3-trimethyl-6-(3- chloropropy1)-bicyclo-[2.2.2]-octan-2-one are added. The reaction mass is then maintained at reflux for a period of 3 hours with moderate stirring. The sodium remains disperseduntil 5 minutes before reflux is discontinued where upon it coagulates into a large ball. The heat source is then removed and stirring is ceased. The reaction mass is decanted from the sodium, acidified to a pH of 3 with 5% of hydrochloric acid and then neutralized to a pH 7 with a sodium bicarbonate solution. The organic layer is separated from the aqueous layer,

and the aqueous layer is extracted four times with ml portions of diethyl ether and vacuum distilled at a temperature of C and a pressure of 0.6 mm. Hg. Mass spectral, IR and NMR analyses yield the data that the major product, obtained in 64% yield, is the title compound having the structure:

Preparation of octahydro-9,9-Dimethyl-1,o-methanonaphthalen-l- (2H )-ol Into a 250 ml three neck flask under helium and equipped with reflux condenser, stirrer, thermometer, and heating mantle, the following materials are placed:

Ingredients Parts by Weight 0.17 gm. 50.00 ml Lithium wirc containing 1% sodium Dicthyl ether (anhydrous) 3.3-DimcthyI-6-(3-chloro-propyl)-bicyc1o- (2.2.2)-octan-2-onc The reaction mass is stirred at reflux for a period of 3% hours. After standing overnight, an additional 50 ml of diethyl ether is added and then 50 ml of water. The ether layer is separated and the water layer is extracted once with diethyl ether. The combined ether layers are dried over anhydrous magnesium sulfate and stripped of solvent yielding an oil having two phases. This oil is redisolved in diethyl ether, redried over anhydrous magnesium sulfate and restripped of solvent yielding 0.9 gm. of oil. GLC /sinches X feet, 10% carbowax, 100C to 220C at 8C per minute), IR and mass spectral analyses yield the information that 22% of the reaction mass is the title material having the structure:

LOH

EXAMPLE XXVIII Diels Alder Reaction Product of 3-hexyn-l-ol and 2,2-dimethyl cyclohexa-3,5-dien-l-one Ingredients Parts by Weight 2.2-Dimethylcyclohexa-3 ,S-dienl-one 3-Hexyn-1-ol Benzene 12.2 grns. (0.10 moles) 19.6 gms. (0.20 moles) 300 mil The ingredients in the autoclave are stirred at a temperature of from 210C up to 230C for a period of 7 hours while the pressure within the autoclave is maintained at 245 pounds per square inch gauge. At the end of the 7-hour period, the autoclave is vented and the benzene is stripped off on a rotary evaporator yielding 31.5 gms. of a dark brown liquid. 4.0 Grams of Primol (U.S. P. white mineral oil available from Exxon, Inc. of Elizabeth, NJ.) and a trace of Ionol (registered trademark of the Shell Chemical Company; butylated hydroxy toluene) is added and the material is rush distilled. The product is fractionated at a vapor temperature of l00-110C at 0.6 mm. Hg. pressure (yield 6.4 grns.). GLC, mass spectral, NMR and IR analyses yield the information that the distilled product is a mixture of two compounds having the following structures:

Analytical Data: Mass spectral analysis: m/e 70, 117, 119, 91, 42, 133, 220 (Parent Peak).

EXAMPLE XXIX A. Preparation of 4-pentyn-l-yl-n-butyl ether using sodium n-butoxide An alcoholic solution of sodium n-butoxide is prepared by adding sodium (47 gms.) to 500 cc of nbutanol. When the reaction is complete, 400 grns. of 4-pentyn-l-iodide is added and the solution heated under reflux for 2 hours. The solution is filtered, the solvent is removed by distillation and the residue is diluted with diethyl ether and washed with water. After drying over anhydrous sodium sulfate, the solvent is evaporated and the residual 4-pentyn-1-yl butyl ether is distilled.

B. Preparation of 4-pentyn-l-yl-n-butyl ether using sodium acetylide To a suspension of 75 gms. of sodium acetylide in one liter of toluene is added 150 gms. of 3-chloropropy1 butyl ether. The mixture is refluxed for 3 hours, cooled and filtered. The solvent is removed under vacuum leaving 165 gms. of a residue which is distilled under vacuum to yield the title product.

EXAMPLE XXX Preparation of 1,3 ,3-trimethyl-6-( 3-n-butoxypropyl )-bicyclo-[2.2.2 octa-S ,7-dien-2-one Into a 2 liter autoclave, the following ingredients are added:

lngredien ts Parts by Weight 2,2,6-Trimethyl cyclohexadienone 20.0 gms. 4-Pentyn-l-yl n-butyl ether (prepared 25.0 gms. according to the process of Example XXIX (A) or XXlX (B) Benzene 300.0 ml

The autoclave is sealed and the reaction mass is stirred for a period of hours at 220C. The reaction mass is then removed from the autoclave and stripped of solvent on a rotary evaporator. A GLC sample of the material shows no 2,2,6-trimethyl-cyclohexadienone remaining 41 inch X 10 feet, 10% carbowax; 80C-220C at 8C/min.). The residue (55 gms.) is

rush distilled on a micro vigreaux column under vacuum, yielding 30 gms. of product. Mass spectal, IR and NMR analyses yield the information that the product is the title compound.

EXAMPLE XXXl Preparation of 1,3 ,3-trimethyl-6-( 3-n-butoxypropyl )-bicyclo-[ 2.2.2 octan-Z-one Into a 2 liter autoclave, the following ingredients are added:

Ingredients Parts by Weight 5% Platinum on carbon, prereduced 0.5 gm. l,3.3-Trimcthyl-6-(3-n-butoxypropyl)- 27.0 gm. bicyclo-l2.2.2]-octa-5,7-dien-2-onc (produced according to Example XXX) lsopropyl alcohol EXAMPLE xxxu Preparation of 1,3,3-trimethyl-6-(3-hydroxypropyl)-bicyclo[2.2.2]- 0ctan-2-one from 1,3,3-trimethyl-6-(3-n-butoxypropyl) bicyclo-[2.2.2]-octan-2-one Into a 500 ml three neck round bottom flask equipped with stirrer, thermometer, reflux condenser, heating mantle and addition funnel is placed the 1,3,3- trimethyl-6-(3-n-butoxypropy1) bicyclo[2.2.2]-octan- 2-one produced according to the process of Example XXXI in 100 ml of aqueous ethanol. 50 ml of concentrated hydriodic acid is then added slowly to the reaction mass over a period of 5 hours while the reaction mass is refluxed. Refluxing is continued for another 3 hours whereupon the solvent and butyl iodide and butanal is stripped off. The resulting residue is distilled under vacuum to yield the 1,3,3-trimethyl-6-(3- hydroxypropyl)-bicyclo-[2.2.2]-octan-2-one (boiling point 148-150C, 1.5 mm. Hg. pressure).

EXAMPLE XXXlIl Ingredients Parts by Weight 1,3,3-Trimethyl-6-(3-hydroxypropyl)- 13.8 gms. bicyelo-l2.2.2l-octan-2one (Produced according to Example XXXII) Benzene 6.0 ml

16 Grams of thionyl chloride is added to the reaction mass over a period of 5 minutes with stirring, the addition causing an exothermic reaction. The reaction mass temperature rises to 55C. Following addition, the mixture is stirred for 3 hours at reflux. The pot temperature is initially 92C at reflux, but rises to C after a period of 3 hours.

After cooling, the mixture is poured onto 100 gms. of ice. The resulting ice mixture is then allowed to warm to room temperature and is then neutralized with sodium bicarbonate and the reaction mass-ice mixture is extracted 4 times with diethyl ether. The combined ether extracts are dried over anhydrous magnesium sulfate and filtered. The ether is then stripped on a rotary evaporator yielding 14.4 gms. of residue. The residue is rush-distilled on a micro-vigreaux column at a temperature of l43l44C at a pressure of 1.2 mm. Hg.

Mass spectral, IR and NMR analyses yield the data that the product is the title compound.

Mass spectral analysis is as follows: m/e 82, 170,-

171, 4k, 242 (Parent Peak).

NMR analysis is as follows: 0.91(s,3H), l.07'(s,3H), 1.1l(s,3H-), 1.4-2.1 (signal for 12H), 3.47 (t,2l-l) ppm.

EXAMPLE XXXIV Synthesis of Dihydronorpatchoulinol Into a 500 ml flask fitted with a condenser, stirrer, thermometer and nitrogen inlet tube, the following materials are placed:

in redients Parts by Weight Xylene ml Sodium 7.5 gm.

The mixture is heated to 90C while stirring vigorously. When the sodium is completely dispersed in fine particles, the stirring is ceased and the heat source is removed after which time the mixture is cooled using an ice bath. When the sodium dispersion temperature reaches 30C, the xylene is decanted and replaced with 50 gms. of tetrahydrofuran. The resulting mixture is refluxed 'and l 1 gms. of 1,3,3-trimethyl-6-(3- chloropropyl)-bicyclo-[2.2.2]-octan-2-one are added. The reaction mass is then maintained at reflux for a period of 3 hours with moderate stirring. The sodium remains dispersed until 5 minutes before reflux is discontinued where upon it coagulates into a large ball. The heat source is then removed and stirring is ceased. The reaction mass is decanted from the sodium, acidified to a pH of 3 with 5% of hydrochloric acid and then neutralized to a pH 7 with a sodium bicarbonate solution. The organic layer is separated from the aqueous layer, and the aqueous layer is extracted four times with 100 ml portions of diethyl ether and vacuum distilled at a temperature of 120 and a pressure of 0.6 mm. Hg. Mass spectral, IR and NMR analyses yield the data that the major product, obtained in 64% yield, is the title compound having the structure:

Mass spectral anaylsis is as follows: m/e 208 (Parent Peak), 41, 84,124, 81.

NMR analysis is as follows: 0.83(s,3H), l.07(s,3H), 1.l0(s,3H), 1.0-2.0 (Complex signals, 14H) ppm.

EXAMPLE XXXV A. Preparation of 4-pentyn-l-yl-benzyl ether from potassium-4-pentyn-1-oxide An alcoholic solution of potassium-4-pentyn-l-oxide is prepared by adding 4-pentyn-1-ol 170 gms.) to a solution of 47 gms. of potassium in 500 cc of 1,2-

. diethoxyethane. 400 Grams of benzyl chloride is added and the solution is heated under reflux until the solution is no longer alkaline to moist litmus paper. The solvent is removed by distillation and the residue is diluted with diethyl ether, washed with water and dilute sodium hydroxide. After drying over anhydrous sodium sulfate, the solvent is evaporated and the residual 4- pentyn-l-yl benzyl ether is distilled.

B. Preparation of 4pentyn-l-yl-benzyl ether from sodium acetylide To a suspension of 75 gms. of sodium acetylide in l liter of toluene is added 184 gms. of 3-ch1or0propyl benzyl ether. The mixture is stirred and refluxed for 3 hours, cooled and filtered. The solvent is removed under vacuum leaving a dark coloredresidue which is vacuum distilled to yield the desired product.

EXAMPLE XXXVI Preparation of l,3,3-trimethyl-6-( 3-benzyloxypropyl)-bicyclo- [2.2.2]-octa-5,7-dien-2-one Into a 2 liter autoclave, the following ingredients are added:

Ingredients Parts by Weight 2,2,6-Trimethyl cyclohexadienone 25.0 gms. 4-Pentyn-l-yl benzyl ether (prepared 15.0 gms. according to Example XXXV (A) or XXXV (B) Benzene 300.0 ml

EXAMPLE XXXVII v Preparation of 1,3 ,3-trimethyl-6-( 3-benzyloxypropyl)-bicyclo- [2.2.2]-octan-2-one Into a 2 liter autoclave, the following ingredients are added:

Ingredients Parts by Weight 5% Platinum on carbon. prereduced 0.5 grns. l,3,3-trimethyl-6-(3-benz loxypropyl)- 25.0 gms. bicyclo[2.2.2]-octa-5,7- ien-2-one (prepared according to Example XXXVI) lsopropyl alcohol 300.0 ml

The autoclave is sealed and pressurized to pounds per square inch with hydrogen. The reaction mass is heated to C and the pressure rises to 220 pounds per square inch. Heating and stirring is continued until GLC or mass spectral analyses indicates reaction is complete (about 20 hours). The autoclave is vented and the reaction mass is filtered and stripped of solvent, yielding 21 gms. of residue. Distillation under vacuum gives the title material.

EXAMPLE XXXVIII Preparation of 1,3 ,3-trimethyl-6-( 3-hydroxypropyl )-bicyclo-[ 2.2.2]- octan-2-one from l,3,3-trimethyl-6-( 3-benzyloxypropyl)-bicyclo- [2.2.2]-octan-2-one Into a 500 ml three neck' round bottom flask equipped with stirrer, thermometer, reflux condenser, heating mantle and addition funnel is placed the 1,3,3-

I hydroxypropyl)-bicyclo-[2.2.2l-octan-2-one.

EXAMPLE XXXIX Preparation of 1,3 ,3-trimethyl-6-( 3-chloropropyl)-bicyclo-[2.2.2 octan-2-one Into a 50 ml flask equipped with reflux condenser, thermometer and addition funnel, the following ingredients are added:

Ingredients Parts by Weight l,3,3-Trimethyl-6-(3-hydroxypropyl)- 12 gms. bicycle-l2.2.21-octan-2-one (produced according to Example XXXVIII) Benzene 6.0 ml

l4 Grams of thionyl chloride is added to the reaction, mass over a period of 5 minutes with stirring, the addition causing an exothermic reaction. The reaction mass temperature rises to 55C. Following addition, the mixture is stirred for 3 hours at reflux. The pot temperature is initially 92C at reflux, but rises to 100C after a period of 3 hours.

After cooling, the mixture is poured onto 100 gms. of

ice. The resulting ice mixture is then allowed to warm to room temperature and is then neutralized with sodium bicarbonate and the reaction mass-ice mixture is extracted 4 times with diethyl ether. The combined ether extracts are dried over anhydrous magnesium sulfate and filtered. The ether is then stripped on a rotary evaporator yielding 14.0 gms. of residue. The residue is rush-distilled on a micro-vigreaux column at a temperature of l43l44C at a pressure of 1.2 mm. Hg. Mass spectral, IR and NMR analyses yield the data that the product is the title compound.

Mass spectral analysis is as follows: m/e 82, 170, 171, 41, 242 (Parent Peak).

NMR analysis is as follows: 0.91 (s,3H), l.O7(s,3H), 1.11 (8,3H), 1.4 2.1 (signal for 12H), 3.47(z,2l-I) PPm.

EXAMPLE XL Synthesis of Dihydronorpatchoulinol Into a 500 ml flask fitted with a condenser, stirrer, thermometer and nitrogen inlet tube, the following materials are placed:

Ingredients Parts by Weight Xylene 15.0 ml Sodium 7.5 gm.

' The mixture is heated to 90C while stirring vigorously. When the sodium is completely dispersed in fine particles, the stirring is ceased and the heat source is removed after which time the mixture is cooled using an ice bath. When the sodium dispersion temperature reaches 30C, the xylene is decanted and replaced with 50 gms. of tetrahydrofuran. The resulting mixture is refluxed and l l gms. of 1,3,3-trimethyl-6-(3- chloropropyl)-bicyclo-[2.2.2]-octan-2-one produced according to Example XXXIX are added. The reaction mass is then maintained at reflux for a period of 3 hours with moderate stirring. The sodium remains dispersed until 5 minutes before reflux is discontinued where upon it coagulates into a large ball. The heat source is then removed and stirring is ceased. The reaction mass is decanted from the sodium, acidified to a pH of 3 with 5% of hydrochloric acid and then neutralized to a pH 7 with a sodium bicarbonate solution. The organic layer is separated from the aqueous layer, and the aqueous layer is extracted four times with ml portions of diethyl ether and vacuum distilled at a temperature of C and a pressure of 0.6 mm. Hg. Mass spectral, IR and NMR analyses yield the data that the major product, obtained in 64% yield, is the title compound having the structure:

Mass spectral analysis is as follows: m/e 208 (Parent Peak),4l,84, 124,81.

NMR analysis is as follows: 0.83(s,3H), 1.07(s,3l-I), l.10(s,3H), 1.0-2.0 (Complex signals), 14H) ppm.

What is claimed is:

l. A compound having the structure:

wherein Z is a moiety selected from the group consisting of R T Ra wherein each of R R R R R R R R R and R is the same or different and each represents a moiety selected from the group consisting of methyl and hydrogen; wherein R is selected from the group consisting of hydrogen, methyl and ethyl and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzloxyl and alkoxyl.

2. The compound of claim 1 wherein each of R R R R R R R R R R and R is hydrogen.

3. The compound of claim 1 wherein each of R R R R and R is methyl and each of R R R R R and R is hydrogen 4. The compound of claim 1 wherein each of R R R R and R is methyl; wherein each of R R R R R and R is hydrogen and wherein X is hydroxyl.

5. The compound of claim 1 wherein R is methyl and each of R R R R R R R R R and R is hydrogen.

6. The compound of claim 1 wherein X is chloro.

7. The compound of claim 1 wherein Z is a moiety having the structure:

8. The compound of claim 1 wherein Z is a moiety having the structure:

9. A mixture of compounds wherein one of the compounds has the structure and the other of the compounds has the structure:

10. A process for producing a compound having the structure:

comprising the step of intimately admixing at a temperature of from 200C. up to 260C. and at autogeneous pressure a cyclohexadienone having the structure:

with an acetylenic compound selected from the group of compounds having the structures:

34 comprising the step of intimately admixing at a temperature of from 200C. up to 260C. and at autogeneous pressure a cyclohexadienone having the structure:

wherein Z is a moiety selected from the group consisting of and wherein each of R R R R R R R R R 3 with an acetylenic compound having the structure: and R is the same or different and each represents a moiety selected from the group consisting of methyl and hydrogen, wherein R is selected from the group consisting of hydrogen, methyl and ethyl and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzyloxyl and alkoxyl.

11. The process of claim 10 wherein each of R R R R R R R R R R and R is hydrogen.

12. The process of claim 10 wherein each of R R R R and R is methyl and each of R R R R R and R is hydrogen.

13. The process of claim 10 wherein each of R R R R and R is methyl; wherein each of R R R R R and R is hydrogen and wherein X is hydroxyl.

14. The process of claim 10 wherein R is methyl and each Of R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is hy' drogen.

15. The process of claim 10 wherein X is chloro.

16. The process for producing a compound having the structure:

whereineach of R R R R R R R R R and R is the same or different and each represents a moiety selected from the group consisting of methyl and hydrogen; wherein R, is selected from the group consisting of hydrogen, methyl and ethyl; and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzyloxyl and alkoxyl.

17. The process of claim 16 wherein each of R R R R R R R R R R and R is hydrogen.

18. The process of claim 16 wherein each of R R R R and R is methyl and each of R R R R R and R is hydrogen.

19. The process of claim 16 wherein each of R R R R and R is methyl and each of R R R R R and R is hydrogen, and wherein X is hydroxyl.

20. The process of claim 16 wherein R is methyl and each of R R R R R R R R R and R is hy- 22. The process of claim 10 wherein Z is the moiety drogen. having the structure:

21. The process of claim 10 wherein Z is the moiety 

1. A COMPOUND HAVING THE STRUCTURE:
 1. A compound having the structure:
 2. The compound of claim 1 wherein each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is hydrogen.
 3. The compound of claim 1 wherein each of R1, R2, R3, R4, and R5 is methyl and each of R6, R7, R8, R9, R10 and R11 is hydrogen.
 4. The compound of claim 1 wherein each of R1, R2, R3, R4 and R5 is methyl; wherein each of R6, R7, R8, R9, R10 and R11 is hydrogen and wherein X is hydroxyl.
 5. The compound of claim 1 wherein R1 is methyl and each of R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is hydrogen.
 6. The compound of claim 1 wherein X is chloro.
 7. The compound of claim 1 wherein Z is a moiety having the structure:
 8. The compound of claim 1 wherein Z is a moiety having the structure:
 9. A mixture of compounds wherein one of the compounds has the structure
 10. A process for producing a compound having the structure:
 10. A PROCESS FOR PRODUCING A COMPOUND HAVING THE STRUCTURE:
 11. The process of claim 10 wherein each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 is hydrogen.
 12. The process of claim 10 wherein each of R1, R2, R3, R4, and R5 is methyl and each of R6, R7, R8, R9, R10, and R11 is hydrogen.
 13. The process of claim 10 wherein each of R1, R2, R3, R4, and R5 is methyl; wherein each of R6, R7, R8, R9, R10, and R11 is hydrogen and wherein X is hydroxyl.
 14. The process of claim 10 wherein R1 is methyl and each of R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is hydrogen.
 15. The process of claim 10 wherein X is chloro.
 16. The process for producing a compound having the structure:
 17. The process of claim 16 wherein each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is hydrogen.
 18. The process of claim 16 wherein each of R1, R2, R3, R4, and R5 is methyl and each of R6, R7, R8, R9, R10 and R11 is hydrogen.
 19. The process of claim 16 wherein each of R1, R2, R3, R4 and R5 is methyl and each of R6, R7, R8, R9, R10 and R11 is hydrogen, and wherein X is hydroxyl.
 20. The process of claim 16 wherein R1 is methyl and each of R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 is hydrogen.
 21. The process of claim 10 wherein Z is the moiety 